Polar effects in free radical reactions. Induced decompositions of peroxo compounds in the substitution of heteroaromatic bases by nucleophilic radicals

Minisci, Francesco; Giordano, Claudio; Vismara, Elena; Levi, Silvio; Tortelli, V.

doi:10.1021/ja00335a048

Cited by 54 publications

(23 citation statements)

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“…In accord with precedents established in previous studies,7b,8b,12,14 a possible mechanism can be proposed (Scheme 2). The first step involves a homolytic cleavage of the C-B bond using one equivalent of manganese(III) acetate.…”

supporting

confidence: 85%

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Direct Alkylation of Heteroaryls Using Potassium Alkyl- and Alkoxymethyltrifluoroborates

2011

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supporting

confidence: 85%

“…6 Within this context, the reactivity of a variety of radical precursors has been studied with quinolines7 and derivatives such as lepidine,8 but the conditions often involve the use of the heteroaryl substrate as a solvent.…”

mentioning

confidence: 99%

Direct Alkylation of Heteroaryls Using Potassium Alkyl- and Alkoxymethyltrifluoroborates

2011

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“…It is seen, in accordance with relation [50), that the smallest BDE(C-C) correspond to the most destabilized substituted ethanes and (or) the most stabilized carbon centered radicals. Some typical values of carbon-carbon bond dissociation energies are given in table xx.…”

Section: Carbon-carbon Bond Breaking and Formingsupporting

confidence: 84%

Substituent Effects in Radical Chemistry

Viehe¹,

Janousek²,

Merényi³

1986

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“…[73] They utilized the resultant sulfate radical anion to perform hydrogen atom abstraction from ethers in analogy to Minisciso riginal method. [69] Theh eterocycle scope is extensive,g oing beyond simple quinolines to more varied 6-membered heteroarenes.Arange of ethers can be successfully employed as radical precursors in the reaction (see selected scope). From ap ractical point of view,t he photoredox conditions obviate the need to heat the reaction, Scheme 18.…”

Section: Hydrogen Atom Abstraction At Sp 3 Hybridized Carbonmentioning

confidence: 99%

Recent Advances in Minisci‐Type Reactions

2019

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Reactions that involve the addition of carbon‐centered radicals to basic heteroarenes, followed by formal hydrogen atom loss, have become widely known as Minisci‐type reactions. First developed into a useful synthetic tool in the late 1960s by Minisci, this reaction type has been in constant use over the last half century by chemists seeking to functionalize heterocycles in a rapid and direct manner, avoiding the need for de novo heterocycle synthesis. Whilst the originally developed protocols for radical generation remain in active use today, they have been joined in recent years by a new array of radical generation strategies that allow use of a wider variety of radical precursors that often operate under milder and more benign conditions. The recent surge of interest in new transformations based on free radical reactivity has meant that numerous choices are now available to a synthetic chemist looking to utilize a Minisci‐type reaction. Radical‐generation methods based on photoredox catalysis and electrochemistry have joined approaches which utilize thermal cleavage or the in situ generation of reactive radical precursors. This review will cover the remarkably large body of literature that has appeared on this topic over the last decade in an attempt to provide guidance to the synthetic chemist, as well as a perspective on both the challenges that have been overcome and those that still remain. As well as the logical classification of advances based on the nature of the radical precursor, with which most advances have been concerned, recent advances in control of various selectivity aspects associated with Minisci‐type reactions will also be discussed.

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Polar effects in free radical reactions. Induced decompositions of peroxo compounds in the substitution of heteroaromatic bases by nucleophilic radicals

Cited by 54 publications

References 1 publication

Direct Alkylation of Heteroaryls Using Potassium Alkyl- and Alkoxymethyltrifluoroborates

Direct Alkylation of Heteroaryls Using Potassium Alkyl- and Alkoxymethyltrifluoroborates

Substituent Effects in Radical Chemistry

Recent Advances in Minisci‐Type Reactions

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